Chao Peng

Hygroscopic Behavior of Multicomponent Aerosols Involving NaCl and Dicarboxylic Acids.

Atmospheric aerosols are usually complex mixtures of inorganic and organic compounds. The hygroscopicity of mixed particles is closely related to their chemical composition and interactions between components, which is still poorly understood. In this study, the hygroscopic properties of submicron particles composed of NaCl and dicarboxylic acids including oxalic acid (OA), malonic acid (MA), and succinic acid (SA) with various mass ratios are investigated with a hygroscopicity tandem differential mobility analyzer (HTDMA) system. Both the Zdanovskii-Stokes-Robinson (ZSR) method and extended aerosol inorganics model (E-AIM) are applied to predict the water uptake behaviors of sodium chloride/dicarboxylic acid mixtures. For NaCl/OA mixed particles, the measured growth factors were significantly lower than predictions from the model methods, indicating a change in particle composition caused by chloride depletion. The hygroscopic growth of NaCl/MA particles was well described by E-AIM, and that of NaCl/SA particles was dependent upon mixing ratio. Compared with model predictions, it was determined that water uptake of the NaCl/OA mixture could be enhanced and could be closer to the predictions by addition of levoglucosan or malonic acid, which retained water even at low relative humidity (RH), leading to inhibition of HCl evaporation during dehydration. These results demonstrate that the coexisting hygroscopic species have a strong influence on the phase state of particles, thus affecting chemical interactions between inorganic and organic compounds as well as the overall hygroscopicity of mixed particles.

Hygroscopic properties of potassium chloride and its internal mixtures with organic compounds relevant to biomass burning aerosol particles

While water uptake of aerosols exerts considerable impacts on climate, the effects of aerosol composition and potential interactions between species on hygroscopicity of atmospheric particles have not been fully characterized. The water uptake behaviors of potassium chloride and its internal mixtures with water soluble organic compounds (WSOCs) related to biomass burning aerosols including oxalic acid, levoglucosan and humic acid at different mass ratios were investigated using a hygroscopicity tandem differential mobility analyzer (HTDMA). Deliquescence points of KCl/organic mixtures were observed to occur at lower RH values and over a broader RH range eventually disappearing at high organic mass fractions. This leads to substantial under-prediction of water uptake at intermediate RH. Large discrepancies for water content between model predictions and measurements were observed for KCl aerosols with 75 wt% oxalic acid content, which is likely due to the formation of less hygroscopic potassium oxalate from interactions between KCl and oxalic acid without taken into account in the model methods. Our results also indicate strong influence of levoglucosan on hygroscopic behaviors of multicomponent mixed particles. These findings are important in further understanding the role of interactions between WSOCs and inorganic salt on hygroscopic behaviors and environmental effects of atmospheric particles.

Enhanced Light Scattering of Secondary Organic Aerosols by Multiphase Reactions

Secondary organic aerosol (SOA) plays a pivotal role in visibility and radiative forcing, both of which are intrinsically linked to the refractive index (RI). While previous studies have focused on the RI of SOA from traditional formation processes, the effect of multiphase reactions on the RI has not been considered. Here, we investigate the effects of multiphase processes on the RI and light-extinction of m-xylene-derived SOA, a common type of anthropogenic SOA. We find that multiphase reactions in the presence of liquid water lead to the formation of oligomers from intermediate products such as glyoxal and methylglyoxal, resulting in a large enhancement in the RI and light-scattering of this SOA. These reactions will result in increases in light-scattering efficiency and direct radiative forcing of approximately 20%-90%. These findings improve our understanding of SOA optical properties and have significant implications for evaluating the impacts of SOA on the rapid formation of regional haze, global radiative balance, and climate change.

Optical properties of secondary organic aerosols derived from long-chain alkanes under various NOx and seed conditions

Long-chain alkanes are a type of important intermediate-volatile organic compounds (IVOCs) in the atmosphere, which contribute to a large proportion of secondary organic aerosol (SOA). However, the optical properties of SOA derived from long-chain alkanes remain poorly understood. Here, we investigate the refractive index (RI) of SOA derived from photo-oxidation of dodecane (C12), pentadecane (C15) and heptadecane (C17) under low-NOx and high-NOx conditions with the absence or presence of inorganic aerosol seeds. The RIs of these SOAs are found to be in the range of 1.33 to 1.57 at the wavelength of 532nm. The results from mass spectroscopy indicate that both reaction mechanisms influenced by NOx level and gas-particle partitioning influenced by seeds have important impact on the chemical compositions of SOAs, which further influence the optical properties like RI. Finally, by comparing the RI values to other literature and model results, we suggest that various RIs of SOAs derived from long-chain alkanes should be applied in atmospheric and climate models.

Effects of Gas-Particle Partitioning on Refractive Index and Chemical Composition of m-Xylene Secondary Organic Aerosol

The formation of secondary organic aerosols (SOAs) contains partitioning processes of the oxidation products between the gas and particle phases, which could change the particle-phase composition when particles grow. However, the effects of these processes on the optical properties of SOA remain poorly understood. In this study, we performed smog chamber experiments to investigate the effects of gas-particle partitioning (GPP) on the refractive index (RI) and chemical composition of the m-xylene SOA. Here, we show that the GPP processes, as organic mass increases, can increase the proportions of semivolatile and intermediate-volatility organic compounds (SVOCs and IVOCs) in the particle phase and result in the decrease of SOA RI real part for 0.09 ± 0.02 (without seeds) and 0.15 ± 0.02 (with seeds). This indicates that the SOA optical properties are closely related to the total organic mass and molecular-level composition. In addition, the presence of inorganic seeds promotes the GPP to the particle phase and hence further decreases the RI real part for 0.05 ± 0.02. As pre-existing aerosols are ubiquitous in the ambient atmosphere, it is suggested that there should be a certain correction when the SOA RI of previous laboratory studies is applied to air quality and climate models.

Hygroscopic behavior of water-soluble matter in marine aerosols over the East China Sea.

In this study, we investigated hygroscopic properties of water-soluble matter (WSM) in marine aerosols over the East China Sea, which were collected during a Natural Science Foundation of China (NSFC) sharing cruise in 2014. Hygroscopic growth factors (g) of WSM were measured by a hygroscopicity tandem differential mobility analyzer (H-TDMA) with an initial dry particle mobility diameter of 100nm. The observed g at 90% relative humidity (RH), g(90%)WSM, defined as the ratio of the particle diameter at 90% RH to that at RH<5% (initial dry diameter), ranged from 1.67 to 2.41 (mean±std: 1.99±0.23). The g values were lower than that of seawater (2.1) but comparable with those reported for marine aerosols (1.79-2.08). The H-TDMA retrieved hygroscopicity parameter of WSM, κWSM, ranged from 0.46 to 1.56 (0.88±0.35). The observed g(90%)WSM during the daytime ranged from 1.67 to 2.40 (1.95±0.21) versus 1.71 to 2.41 (2.03±0.26) during the nighttime. κWSM was 0.81±0.32 in the daytime and 0.95±0.40 in the nighttime. The day/night differences of g(90%)WSM and κWSM indicated that nighttime marine aerosols were more hygroscopic than those in daytime, which was likely related to enhanced heterogeneous reaction of ammonium nitrate in nighttime and the higher Cl-/Na+ molar ratios obtained (0.80) in nighttime than those (0.47) in daytime. Inorganic ions accounted for 72-99% of WSM with SO42- being the dominant species, contributing to 47% of the total inorganic ion mass. The declined g(90%) comparing with sea water was likely due to the transport of anthropogenic aerosols, chemical aging of dust particles, the contribution of biomass burning products, and the aerosol hygroscopic growth inhibition of organics.

Characterization of water soluble inorganic ions and their evolution processes during PM2.5 pollution episodes in a small city in southwest China

PM2.5 samples were collected in four segregate one-month periods, each representing one season, for analyzing their contents of water soluble inorganic ions (WSIIs) in a small city inside Sichuan Basin. Daily PM2.5 concentrations ranged from 23.2 to 203.1 μg m-3 with an annual mean of 66.9 ± 33.6 μg m-3. Annual mean concentrations of WSIIs was 28.8 ± 20.3 μg m-3, accounting for 43.1% of PM2.5. Seasonal mean concentrations of WSIIs ranged from 17.5 ± 9.3 μg m-3 in summer to 46.5 ± 27.6 μg m-3 in winter. Annual mean mass ratio of NO3-/SO42- was 0.49, demonstrating predominant stationary sources for secondary inorganic aerosols (SNA, including SO42-, NH4+ and NO3-); whereas annual mean molar ratio of [NH4+]/[NO3-] was 3.5, suggesting dominant agriculture emissions contributing to the total nitrogen. During a severe and long-lasting (13 days) winter pollution period when mean PM2.5 concentration reached to 132.5 μg m-3, PM2.5 concentration was enhanced by a factor of 2.6 while that of SNA by a factor of 2.9 compared to those before the pollution event, and the fraction of SNA in PM2.5 only increased slightly (from 46.7% to 50.6%). Thus, local accumulation of pollutants under poor diffusion conditions played a major role causing the extremely high PM2.5 concentration, besides the contributions from the enhanced SNA formation under specific weather conditions.

Development and application of the multi-wavelength cavity ring-down aerosol extinction spectrometer

To better characterize the optical properties of atmospheric aerosols, the multi-wavelength cavity ring-down aerosol extinction spectrometer (MCRD-AES) is developed and applied in this study. By using tunable light source and four parallel cavities, the MCRD-AES covers a wide and atmospherically relevant wavelength range from 360 to 663 nm. Four wavelengths (375 nm, 440 nm, 532 nm, and 620 nm) are particularly tested with ammonium sulfate and nigrosine. The refractive index values obtained from this study agree well with literature data. The stability and accuracy of the MCRD-AES are tested, and the minimum detectable extinction coefficient is 0.5 1/Mm. The high sensitivity, high precision, and wavelength changeable of MCRD-AES indicate its great application prospect in comprehensively quantifying the optical properties of atmospheric aerosols.

Effect of Titanium Dioxide on Secondary Organic Aerosol Formation

Secondary organic aerosol (SOA), a dominant air pollutant in many countries, threatens the lives of millions of people. Extensive efforts have been invested in studying the formation mechanisms and influence factors of SOA. As promising materials in eliminating air pollutants, the role of photocatalytic materials in SOA formation is unclear. In this study, TiO2 was employed to explore its impact on SOA formation during the photooxidation of m-xylene with NO x in a smog chamber. We found that the presence of TiO2 strongly suppressed SOA formation. The yields of SOA in the photooxidation experiments of m-xylene with NO x were 0.3-4%, whereas negligible SOA was formed when TiO2 was added. When ((NH4)2SO4) was introduced as seed particles, the presence of TiO2 decreased the yields of SOA from 0.3-6% to 0.3-1.6%. The sharply decreased concentrations of reactive carbonyl compounds were the direct cause of the suppression effect of TiO2 on SOA formation. However, the suppression effect was influenced by the addition of seed particles and the initial concentration of NO x. Reaction mechanisms of the photocatalysis of m-xylene with and without NO x were proposed.